Ethynylene containing n-phenyl carbamates

ABSTRACT

COMPOUNDS OF THE FORMULA   (R,R1,R2,R3,R4-PHENYL)-NH-COO-Y-C*C-R5   IN WHICH R IS (E) HYDROXY, OR (A) HYDROGEN, (F) ALKOXY, (B) ALKYL, R2 IS (C) NITRO, (A) HYDROGEN, (D) HALO, (B) METHYL, (E) HYDROXY, (C) HALO, OR (F) ALKOXY, (D) ALKOXY, (G) ALKYLTHIO, OR R3 IS (H) PHENYL, (A) HYDROGEN, R1 IS (B) METHYL, OR (C) HALO, (A) HYDROGEN, R4 IS (B) ALKYL, (A) HYDROGEN, (C) NITRO, (B) METHYL, OR (D) HALO, (C) HALO, Y IS A DIVALENT LOWER ALKENYL, LOWER ALKYNYL OR LOWER ALKYL RADICAL EITHER STRAIGHT OR BRANCHED CHAIN, AND R5 IS AN ALKYL, CYCLOALKYL OR ALKENYL GROUP AND THEIR USE AS ACARICIDES AND INSECTICIDES.

United States l atent Oifice 3,660,465 Patented May 2, 1972 US. Cl. 260-471 C 2 Claims ABSTRACT OF THE DISCLOSURE Compounds of the formula in which R is (a) hydrogen, y (c) nitro, (d) halo, y y, (f) alkoxy, (g) alkylthio, or (h) phenyl, e R is (a) hydrogen, (b) alkyl, nitro, (d) halo, (c) hydroxy, or (f) alkoxy, R is (a) hydrogen, (b) methyl, (0) halo, or (d) alkoxy, R is (a) hydrogen, (b) methyl, or (c) halo, R is v.

(a) hydrogen, (b) methyl, or (c) halo, Y is a divalent lower alkenyl, lower alkynyl or lower alkyl radical either straight or branched chain, and R is an alkyl, cycloalkyl or alkenyl group and their use as acaricides and insecticides.

This is a continuation-in-part of application Ser. No. 717,970, filed Apr. 1, 1968.

This invention relates to certain novel ethynylene containing N-phenyl carbamates and to their use as acaricides and insecticides.

Acarids, especially mites, are a serious problem in agriculture and horticulture. They are widely distributed throughout the world and in the United States they are known to attack a wide variety of plants, poultry and livestock. Few other pests cause greater damage to so wide a range of hosts.

A considerable assortment of acaricidal materials have been suggested and investigated for the control of the acarid organisms. It is also known that certain organisms are capable of development resistance to certain classes of acaricides. Therefore, there exists a continuing search for new materials to control the aforementioned pests, wherein the capability to establish resistance is decreased and satisfactory control can be realized.

The compounds of the present invention are especially valuable as acaricides because they have little or no phytotoxic properties. Thus, acarids that host on plants can be controlled without injury to the plant.

The compounds of this invention are those of the formula in which R is selected from the group consisting of (a) hydrogen, (b) alkyl, preferably 1 to 4 carbon atoms, (c) nitro, (d) halo, (e) hydroxy, (f) alkoxy, preferably 1 to 4 carbon atoms, (g) alkylthio, preferably 1 to 4 carbon atoms, more preferably methylthio, or (h) phenyl, preferably 4-phenyl, R is selected from the group consisting of (a) hydrogen, (b) alkyl, preferably 1 to 4 carbon atoms, more preferably methyl, (c) nitro, (d) halo, (e) hydroxy, or (f) alkoxy, preferably 1 to 4 carbon atoms, more preferably methoxy, R is selected from the group consisting of (a) hydrogen, (b) methyl, (c) halo, or ((1) alkoxy, preferably 1 to 4 carbon atoms, more preferably methoxy, R is selected from the group consisting of (a) hydrogen, (b) methyl, or (c) halo, R is selected from the group consisting of (a) hydrogen, (b) methyl, or (c) halo Y is a divalent lower alkyl, lower alkenyl or lower alkynyl, either radical straight or branched chain, preferably having from 1 to 6 carbon atoms, most preferably Y is methylene, and R is a member selected from the group consisting of alkyl, preferably having from 1 to 8 carbon atoms, cycloalkyl, preferably cyclohexyl and alkenyl, preferably having from 2 to 4 carbon atoms, most preferably R is methyl.

Representative compounds of this invention are: R1 4-chlorophenylcarbamyloxy-Z-butyne 4-chlorophenylcarbamyloxy-Z-pentyne 2 i 9 Y 4-chlorophenylcarbamyloxy-2-hexyne R R3 R W 4-chloropheny1carbamyloxy-3-pentyne 5 1 H o 4-chlorophenylcarbamyloxy-4-hexyne R 5 2-chlorophenylcarbamyloxy-Z-butyne N-C-O-Y-CEC-R. 3-chlorophenylcarbamyloxy-Z-butyne 4, 4-bromophenylcarbamyloxy-2-butyne 4-fluorophenylcarbamyloxy-2-butyne 1O 1n which R, R R R R Y and R are defined as above. gj'gl fi i fi fi i z g fi igi jigggg The molar ratio of the reactants may fall within the t z n range of from about 0.5 to 2 moles isocyanate per mole i g g g 10x Y j ne of the alcohol; however, in preferred operation, the stoi- 2 23 5 2 nylgarbamylgxy g butyni 15 chiometric molar ratio of 1 mole isocyanate per mole of the alcohol is employed. g:253$f igfggggaggsgggzigigjggfigi The reaction temperature may vary over a wide range, 3 chloro 4 meth 1 hen lcarbamyloxyabutyne 1.e., from about C. up to the boillng polnt of the 2 m 4 nitroyhpen lzarbam 10X n6 reaction mixture. In preferred operation, however, reac- 4: C hl8;g:2:nitroPhenY1carbam loxlczbutzne {)0 tion temperatures from about room temperature up to 2 h d h 3 10 5 3 n about 60 C. are employed. The reaction 15 of an exoi thermic nature, and the time of reaction may vary over a wide range. Highest yields are secured, however, with y g g y e a reaction time of from about /2 to 1 hour. Preferably, g gi g the reaction should be run under anhydrous conditions. z g 0 It is desirable to employ a suitable solvent in order '3; f i i g' t to facilitate the obtainment of a homogeneous reaction 1 z i mixture and also to secure ease of reaction. Any solvent 2231 He may be utilized provided it is a solvent for the reactants, if g E y 30 and is inert under the conditions of reaction. Ether, ben- 'i g gg' 'gi gg zg zgi g g gg 2 g: zene, chloroform, and carbon tetrachloride are useful as a solvent. j' ig P ggg gggg ig' gg n Preferably catalytic amounts of such catalysts are di- 'g i g 2 g gi i tg g i i 2 butyne butyl tin dilaurate and triethyl amine or mixtures thereof should be used. gig'gi gfg g ig iglg gfg fg The reaction products can be recovered and purified, fi g ffig i g g e if necessary, by conventional means well-known to those 2,3,4,5-tetrafluorophenylcarbamyloxy-2-butyne skilled m the 2,3,5,6-tetrafiuorophenylcarbamyloxy-Z-butyne EXAMPLE I 4'n'butylphenylcarbamyloxy'z'butyne 4O 4-chlorophenylcarbamyloxy-2-butyne The most referred com ounds are 4-chloro hen lcarbamyloxy-2 butyne whiclFhas the formula P y 2 grams (0'25 mole.) i' 2 dlops (.hbutyl H 0 tin dilaurate, 4 drops triethyl amine are mixed 1n 150 I U ml. dry ethyl with vigorous stirring in a flask. 38.6 grams C1N-C-0-CH -Q?- C-CH 45 (0.25 mole) p-chlorophenyl isocyanate dissolved in 100 ml. of dry ether is added slowly to the flask with some and 2,4-dichlorophenylcarbamyloxy-Z-butyne, which has exothermic reaction and is heated at reflux for /2 hour. the formula The reaction mixture is then cooled and the white reaction C1 H 0 product precipitated. The product is recovered and washed H 5 with hexane, M.P. l24-l26 C. The yield is 44.1 grams. C1 Q Analysis of the product is in agreement with the structure of the title compound. The compounds of this invention can be prepared ac- Table I lists other compounds that are prepared accordcording to the following reaction ing to the procedure described in Example I.

TABLE I Compound N or number R R R R R Y R M.P. c

1 4-chloro H H H CH2 CH3- 124-126 2 4-cl1loro 34shloro H H H CH2- CH3 116-118 4-bromo.-- H H H -CHz OH3- 129-131 H H -CHz cHa- 89-90 H H CH2- CH3 73-75 H H -CH2- 0111- 72-74 H H CH2 CH1 1.5562 H H CH2 CH.1-- 68-69 H H -CH7 0133- 61-63 H H CH2 CHa- 44-46 H H CH2- CHa 1. 5373 H H CH2 0112- 56-58 H H CH2 oH1- 113-115 H H CHz cH1- 104-106 H H cH- CHg- 102-105 H H CH2 CH3- 49-51 H H CH2 0117- 101-103 H H CH2- CH:- 125.5-1275 H H -cH2- CHz- 112-114 H H CHz- CH 93-95 H H CH2- CH3 88-91 H H CH2- CH3 -62 H H CH2 CH3- 92-04. H H -oH1- oH= 72-74 6 Prepared in Example I.

ACARICIDAL EVALUATION TEST The two-spotted mite, Tetranychus telarius (Linn), was employed in tests for acaricides. Young pinto bean plants in the primary leaf stage were used as the host plants. The young pinto bean plants were infested with several hundred mites. Dispersions of candidate materials were prepared by dissolving 0.1 gram in ml. of a suitable solvent, usually acetone. Aliquots of the toxicant solutions were suspended in water containing 0.0175 v./v. Sponto 221, an emulsifying agent, the amount of water being sufiicient to give concentrations of active ingredient ranging from 0.25% to 0.001%. The test suspensions were then sprayed on the infested pinto bean plants. After seven days, mortalities of post-embroyonic and ovicidal forms were determined. The percentage of kill was determined by comparison with control plants which had not been sprayed with the candidate compounds. The LD-50 value was calculated using well-known procedures. These values are reported under the columns PE and Eggs in Table II.

TABLE II Aearieidal activity ompound Number PE Eggs 0. 003 0. 008 0. 5 0. 5 0. 01 0. 01 0. 03 0. 03 0. 05 0. 05 0. 03 0. 03 0. 05 0. 03 O. 03 0. O3 0. O5 0. 03 0. 03 0. 03 0. 03 0. 03 0. 03 0. 03 0. 03 0. 03 0. 03 0. 03 0. 008 0. 05 0. 05 0. 05 0. 01 0. 05 0. 01 0. 05 0. 005 0. 05 0. 005 0. 03 0. 003 0. 01 0. 03 0. 03 0. 03 0. 03 0. 03 0. 03

INSECTICIDAL EVALUATION TEST Leaves of curled dock, Rumex crispus, which contain masses of eggs of the dock beetle, Gostroidea cyanea, are dipped in various concentrations by weight of a candidate chemical compound suspended in water. Untreated and treated leaves are placed in separate Petri dishes which contain moistened filter paper and after one week, they are observed for the presence of newly emerged larvae. The LD-SO values are calculated. Results of the test are tabulated in Table III.

6 TABLE III.-PERCENT EMERGENCE OF DOCK BEETLE LARVAE emergence of the larvae is observed with the untreated leaves, which are used as a control.

Various techniques or methods can be employed for contacting mites or insect eggs with the carbamate compounds. For example, spray formulations can be prepared by dissolving the carbamate in suitable organic solvent such as toluene, xylene, benzene and the like, and subsequent dispersion of this solution in water in the presence of a surface active wetting or emulsifying agent. Another method by which the acaricidal or insecticidal agents of the present invention can be applied is in the form of dispersible powders, preferably as homogeneous free-flowing dusts commonly formulated by mixing the active component with finely divided solids or carriers such as talc, natural clays, diatomaceous earth, various flours such as walnut shell, wheat and the like. The details of compounding and application are Well-known to those skilled in the art.

I claim:

1. The compound having the formula 2. The compound having the formula III 0 It N-C-OCH2-C:C-CH3 References Cited UNITED STATES PATENTS 3,127,408 3/1964 Hopkins 260-471 C 3,253,904 5/1966 Harrison 260-471 C 3,226,426 12/1965 Hopkins et al 260-471 C LORRAINE A. WEINBERGER, Primary Examiner L. A. THAXTON, Assistant Examiner US. Cl. X.R. 

